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Laser Induced Breakdown Spectroscopy (LIBS) has become a very popular technique for elemental analysis thanks to its ease of use. However, LIBS users often report poor repeatability of the signal, due to shot-to-shot fluctuations, and consequent not satisfactory limits of detection. In many practical cases, these shortcomings are difficult to control because the signal is affected by several noise sources that cannot be reduced simultaneously. Hopefully, there is a large amount of knowledge, accumulated during several decades, that can provide guidelines to reduce the effect of the single sources of fluctuations. Experimental setup and measurement settings can be optimized on purpose. Spectral data can be processed in order to better exploit the information contained. In the current paper several approaches to improve the analytical figures-of-merit are reviewed and the respective advantages and drawbacks are discussed. [ABSTRACT FROM AUTHOR]

Understanding the mechanisms of the signal enhancement in double-pulse laser-induced breakdown spectroscopy is highly desirable. It is evident, however, that it is not possible to fit a unique general model to the observations obtained in collinear or in orthogonal geometries, in pre-spark or in re-heating schemes, using ns or fs pulses, in a gas or liquid environment. We believe, instead, that by considering separately the specific experimental cases (for example: a given irradiation geometry, a given pulse timing, etc.) the comprehension of the processes occurring during double-pulse experiments might become easier. We focus on one specific experimental case, namely ns double-pulse irradiation of solid targets in a gaseous environment, and classify the experiments according to the irradiation mode orthogonal pre-spark, collinear and orthogonal re-heating). Then, we propose a description of the processes occurring in the different cases, on the basis of data and interpretations that are available in the literature. [ABSTRACT FROM AUTHOR]

Abstract: Palladium nanoparticles are arousing an increasing interest because of their strong activity in heterogeneous catalysis in a wide range of reactions. Driven by the interest of producing Pd nanoparticles to be deposited for catalysis over hydrophobic supports, we investigated their synthesis via Pulsed Laser Ablation in Liquid in several organic solvents, as acetone, ethanol, 2-propanol, toluene, n-hexane. The colloids were produced by using a Nd:YAG ns laser and without the addition of surfactant agents. The morphology, composition, stability and oxidation state of the obtained nanoparticles were investigated by TEM-EDS analysis, UV–vis spectroscopy, X-ray Photoelectron Spectroscopy and micro-Raman spectroscopy. The results evidence that the nature of the solvent influences both the yield and the physico-chemical properties of the produced nanoparticles. While in acetone and alcohols spheroidal, non aggregated and stable particles are obtained, in case of toluene and n-hexane few unstable particles surrounded by a gel-like material are produced. Raman/XPS measurements suggest the presence of amorphous or graphitic carbon onto crystalline Pd nanoparticles, which could have hindered their growth and determined the observed smaller sizes if compared to nanoparticles produced in water. The stability of Pd colloids obtained in acetone and alcohols was attributed to adsorbed anions like enolates or alcoholates; non polar solvents like toluene and n-hexane, unable to give rise to adsorbed anionic species, cannot provide any stabilization to the palladium nanoparticles. XPS analyses also evidenced a partial oxidation of particles surface, with a ratio Pd2+:Pd0 of 1:2.5 and 1:4 in acetone and ethanol, respectively. [Copyright &y& Elsevier]

Abstract: In this work we compare the analytical results obtained by traditional calibration curves (CC) and multivariate Partial Least Squares (PLS) algorithm when applied to the LIBS spectra obtained from ten brass samples (nine standards of known composition and one ‘unknown’). Both major (Cu and Zn) and trace (Sn, Pb, Fe) elements in the sample matrix were analyzed. After the analysis, the composition of the ‘unknown’ sample, measured by X-ray Fluorescence (XRF) technique, was revealed. The predicted concentrations of major elements obtained by rapid PLS algorithms are in very good agreement with the nominal concentrations, as well as with those obtained by the more time-consuming CC approach. A discussion about the possible effects leading to discrepancies of the results is reported. The results of this study open encouraging perspectives towards the development of cheap LIBS instrumentation which would be capable, despite the limitations of the experimental apparatus, to perform fast and precise quantitative analysis on complex samples. [ABSTRACT FROM AUTHOR]

Abstract: The mass removal mechanisms occurring during the ablation of an aluminum target, induced by an Nd:YAG laser at λ =1064 nm in air at different laser fluences, were investigated at different pressures and in the orthogonal double pulse configuration. Both the spectroscopic analysis of the plasma emission and the microscopic analysis of the craters, providing complementary information on the laser ablation process, were performed. The first technique allowed the calculation of the plasma thermodynamic parameters and an estimation of its atomized mass, while the latter led to the calculation of their volume, as well as a qualitative inspection of the craters profile and appearance. The results obtained at different fluences suggest a complex picture where the air pressure strongly drives the laser shielding effect, which in turn affects the relevance of melt displacement, melt expulsion and phase explosion mechanisms. The measurements performed in double pulse configuration suggest that in this case the ablation process is very similar to that induced at low air pressure. Phase explosion seems to occur in double pulse laser ablation while it seems inhibited in single pulse ablation at atmospheric pressure. Differently, melt splashing is much more efficient in single pulse ablation at atmospheric pressure than in double pulse ablation. [Copyright &y& Elsevier]

Limits of detection have been studied for several elements in aluminium and steel alloys, at atmospheric pressure in air, by use of the single and collinear double-pulse configurations of laser-induced breakdown spectroscopy. For this purpose, calibration plots were constructed for Mg, Al, Si, Ti, Cr, Mn, Fe, Ni, and Cu using a set of certified aluminium alloy samples and a set of certified steel samples. The investigation included optimization of the experimental conditions to furnish the best signal-to-noise ratio. Inter-pulse delay, gate width, and acquisition delay were studied. The detection limits for the elements of interest were calculated under the optimum conditions for the double-pulse configuration and compared with those obtained under the optimum conditions for single-pulse configuration. Significantly improved detection limits were achieved, for all the elements investigated, and in both aluminium and steel, by use of the double-pulse configuration. The experimental findings are discussed in terms of the measured plasma conditions (particle and electron density, and temperature). [ABSTRACT FROM AUTHOR]

Abstract: Laser-induced breakdown spectroscopy (LIBS) is a promising technique for in situ environmental analysis. The potential of this technique for accurate quantitative analysis could be greatly improved using an innovative experimental setup – based on the use of two laser pulses suitably retarded – and analyzing the results with a standard-less procedure which overcomes the problems related to matrix effects. A new mobile instrument for soil analysis, developed at the Applied Laser Spectroscopy Laboratory in Pisa, is presented, and some experimental results are given. [Copyright &y& Elsevier]

Twelve archaeological copper objects from the burial site of “Fontino” cave, near Grosseto, (around 2500–2000 B.C.) were analysed using laser-induced breakdown spectroscopy. Qualitative results and a preliminary study of the samples’ composition are reported and used to make a quantitative estimate; based on these results, the samples were classified using principal components statistical analysis. The perspectives of using laser-induced breakdown spectroscopy for archaeometric analysis are also discussed. [ABSTRACT FROM AUTHOR]

In this paper a review of different approaches for handling the self-absorption effect in Laser-Induced Breakdown Spectroscopy (LIBS) applications is presented. From an analytical point of view, self-absorption is a major issue affecting the accuracy of LIBS quantitative analysis. Self-absorption impacts emission line profiles and intensities, resulting in non-linear calibration curves and influencing the estimation of the sample composition. The main purpose of this work is presenting a summary of the experimental parameters giving raise to self-absorption and a thorough study of the different strategies for its estimation, compensation and exploitation in order to improve the analytical accuracy of the LIBS technique. Unlabelled Image • some approaches to estimate the self-absorption degree of spectral lines are reviewed, • the effects of the experimental parameters in LIBS plasmas are discussed, • we review exploitation of self-absorbed lines for diagnostics or quantitative analysis. [ABSTRACT FROM AUTHOR]

• Characterization of LIP by the Columnar Density Saha-Boltzmann (CD-SB) plot. • Use of strongly self-absorbed lines to calculate the plasma temperature. • Temporal evolution of the plasma temperature by CD-SB plot. • CD-SB plot as a promising method to obtain plasma temperature at later times. • CD-SB plot does not require the calibration of the detection system. In exploiting the analytical capabilities of plasma-based spectroscopy method, the evaluation of plasma parameters, particularly the plasma temperature, is a crucial step. In this work, a modified Saha-Boltzmann plot, which uses the columnar densities of atomic and ionic ground levels, is utilized to calculate the plasma temperature in a laser-induced plasma from an aluminum alloy target. The columnar densities are here calculated by quantifying the self-absorption of resonance lines. It is demonstrated that this is a promising method for accurate determination of plasma temperature. To validate the capability of this technique, plasma emission is measured at different gate delay times. For each delay, excitation temperature is calculated both by the conventional Saha-Boltzmann plot (by using the excited states) and by exploiting the new Columnar Density Saha–Boltzmann (CD-SB) plot. The results suggest that at later times of the plasma evolution, the CD-SB plot can be more suitable for the determination of plasma temperature than conventional Saha-Boltzmann plot. These findings provide a new approach for physical characterization of plasmas and give access to a wealth of information about the state of plasma. [ABSTRACT FROM AUTHOR]

The interaction of ultraintense laser pulses with solids is largely affected by the plasma gradient at the vacuum–solid interface, which modifies the absorption and ultimately, controls the energy distribution function of heated electrons. A micrometer scale-length plasma has been predicted to yield a significant enhancement of the energy and weight of the fast electron population and to play a major role in laser-driven proton acceleration with thin foils. We report on recent experimental results on proton acceleration from laser interaction with foil targets at ultra-relativistic intensities. We show a threefold increase of the proton cut-off energy when a micrometer scale-length pre-plasma is introduced by irradiation with a low energy femtosecond pre-pulse. Our realistic numerical simulations agree with the observed gain of the proton cut-off energy and confirm the role of stochastic heating of fast electrons in the enhancement of the accelerating sheath field. [ABSTRACT FROM AUTHOR]